Method for dyeing keratinous material, comprising the use of an organosilicon compound, an oligoalkylsiloxane and a dyeing compound

ABSTRACT

The subject of the present disclosure is a process for dyeing keratinous material, in particular human hair, including the following steps:Application of an agent (a) to the keratinous material, wherein the agent (a) isat least one organic silicon compound selected from silanes having one, two or three silicon atoms, said organic silicon compound including one or more hydroxyl groups and/or hydrolysable groups per molecule, and said agent (a) further including at least one oligoalkylsiloxane, andApplication of an agent (b) to the keratinous material, the agent (b) including at least one colorant compound selected from the group including pigments and/or direct dyes.A second object of the present disclosure is a multi-component packaging unit which contains the two agents (a) and (b) in two separately assembled containers.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a U.S. National-Stage entry under 35 U.S.C. § 371 based on International Application No. PCT/EP2019/063192, filed May 22, 2019, which was published under PCT Article 21(2) and which claims priority to German Application No. 10 2018 213 813.3, filed Aug. 16, 2018, which are all hereby incorporated in their entirety by reference.

TECHNICAL FIELD

The subject of the present application is a process for dyeing keratinous material, especially human hair, which includes the application of at least two different agents (a) and (b). The agent (a) contains at least one organic silicon compound and at least one oligoalkylsiloxane. The agent (b) includes at least one colorant compound selected from the group including pigments and/or direct dyes.

The second subject-matter of this application is a multi-component packaging unit (kit-of-parts) for coloring keratinous material, in particular human hair, which includes the agents (a) and (b) separately packaged in two different containers.

BACKGROUND

Changing the shape and color of keratinous material, especially human hair, is an important area of modern cosmetics. To change the hair color, the expert knows various coloring systems depending on the coloring requirements. Oxidation dyes are usually used for permanent, intensive dyeing's with good fastness properties and good grey coverage. Such colorants contain oxidation dye precursors, so-called developer components and coupler components, which, under the influence of oxidizing agents such as hydrogen peroxide, form the actual dyes among themselves. Oxidation dyes are exemplified by very long-lasting dyeing results.

When direct dyes are used, ready-made dyes diffuse from the colorant into the hair fiber. Compared to oxidative hair dyeing, the dyeing's obtained with direct dyes have a shorter shelf life and quicker wash ability. Dyeing with direct dyes usually remain on the hair for a period of between about 5 and about 20 washes.

The use of color pigments is known for short-term color changes on the hair and/or skin. Color pigments are generally understood to be insoluble, coloring substances. These are present undissolved in the dye formulation in the form of small particles and are only deposited from the outside on the hair fibers and/or the skin surface. Therefore, they can usually be removed again without residue by a few washes with detergents containing surfactants. Various products of this type are available on the market under the name hair mascara.

If the user wants particularly long-lasting dyeing's, the use of oxidative dyes has so far been his only option. However, despite numerous optimization attempts, an unpleasant ammonia or amine odor cannot be completely avoided in oxidative hair dyeing. The hair damage still associated with the use of oxidative dyes also has a negative effect on the user's hair. A continuing challenge is therefore the search for alternative, high-performance dyeing processes.

EP 2168633 B1 deals with the task of producing long-lasting hair colorations using pigments. The paper teaches that when a combination of pigment, organic silicon compound, hydrophobic polymer and a solvent is used on hair, it is possible to create colorations that are said to be particularly resistant to shampooing. For example, 3-aminopropyl-triethoxysilane was used as organic silicon compound.

In WO 2018/115059 A1 a dyeing process is described, which runs in several steps. One step involves the application of an organosilane, and another step involves the application of a direct-pull dye to the hair. This process is also used to achieve dyeing's with good wash fastness properties. The silanes used in this writing are for example 3-aminopropyltriethxoysilane and methyltrimethoxysilane.

In the dyeing processes of EP 2168633 B1 and WO 2018/115059 A1, organosilicon compounds from the group of silanes are used, the molecular structure of these silanes including at least one hydroxy group and/or hydrolysable group. Due to the presence of hydroxy groups or hydrolysable groups, silanes are reactive substances that hydrolyze or oligomerize or polymerize in the presence of water. When applied to the keratin material, the oligomerization or polymerization of the silanes initiated by the presence of water ultimately leads to the formation of a film which fixes the coloring compounds and thus produces very long-lasting colorations.

A closer examination of the dyeing processes disclosed in EP 2168633 B1 and WO 2018/115059 A1 has shown that the timing of film formation is essential for the quality of the color result. It has been found that optimum dyeing results can only be obtained if the formation of the film is precisely matched to the time of application.

If the oligomerization or polymerization of the silanes takes place too early or too quickly, large conglomerates already form in the container. In this case, the formulation containing the silanes already gels in the vessel in which it is provided. The production of intensive or long-lasting colorings is no longer possible this way.

On the other hand, too slow oligomerization or polymerization is also disadvantageous about the color result, because if the film cannot form from the keratinous material with sufficient speed, the fixation of the coloring compounds on the keratin also does not take place or only to an incomplete extent. The consequence of too slow polymerization is therefore too weak color intensities and a much too fast wash-out of the coloring.

A major challenge in dyeing processes with silanes therefore remains the matching of the polymerization rate to the dyeing process. To a first approximation, there is a direct correlation between the speed of polymerization and the water content of the colorant. The higher the water content, the faster the silanes polymerise.

However, further dyeing tests have shown that the sensitivity of the silanes to water is so high that even traces of atmospheric moisture can initiate premature hydrolysis. If the silanes are decanted without a protective gas, for example, even brief contact with moisture from the air is sufficient to initiate hydrolysis that begins far too early. The storage stability of the containers produced in humid air is therefore poor.

BRIEF SUMMARY

The purpose of the present inventive efforts was to provide a dyeing system with fastness properties comparable to those of oxidative dyeing. Wash fastness properties should be outstanding, but the use of oxidation dye precursors normally used for this purpose should be avoided. A technology was sought that would make it possible to fix colorant compounds known from the prior art (such as pigments or direct-acting dyes) to the hair in an extremely durable manner. The production of the dyes should be inexpensive and the dyes themselves should have particularly good storage stability. When using the agents in a dyeing process, consistently good color results should be achievable regardless of the conditions prevailing during production and application (such as humidity and temperature).

Surprisingly, it has now turned out that the above-mentioned task can be excellently solved if keratinous materials, especially hair, are dyed using a procedure in which at least two agents (a) and (b) are applied to the keratinous materials (hair). In this case, the agent (a) contains at least one organic silicon compound (from the group of reactive silanes) and additionally at least one oligoalkylsiloxane. The agent (b) contains at least one coloring compound from the group of pigments and direct dyes. When both agents (a) and (b) were used in a dyeing process, keratinous fibers could be dyed to a consistently high color intensity regardless of the conditions prevailing during manufacture and application. In addition, the wash fastness of the hair dyed with (a) and (b) was excellent.

DETAILED DESCRIPTION

The following detailed description is merely exemplary in nature and is not intended to limit the disclosure or the application and uses of the subject matter as described herein. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description.

A first object of the present disclosure is a method for coloring keratinous material, in particular human hair, including the following steps:

-   -   Application of an agent (a) to the keratinous material, wherein         the agent (a) contains at least one organic silicon compound         selected from silanes having one, two or three silicon atoms,         wherein the organic silicon compound includes one or more         hydroxyl groups and/or hydrolysable groups per molecule, and         wherein the agent (a) further contains at least one         oligoalkylsiloxane, and     -   Application of an agent (b) to the keratinous material, the         agent (b) containing at least one coloring compound from the         group of pigments and/or direct dyes.

Keratinic Material

Keratinous material includes hair, skin, nails (such as fingernails and/or toenails). Wool, furs, and feathers also fall under the definition of keratinous material. Suitably, keratinous material is understood to be human hair, human skin, and human nails, especially fingernails and toenails. Keratinous material is understood to be human hair.

Agent (a) and (b)

In the procedure as contemplated herein, agents (a) and (b) are applied to the keratinous material, in particular human hair. The two means (a) and (b) are different.

In other words, a first subject of the present disclosure is a process for dyeing keratinous material, in particular human hair, including the following steps:

-   -   Application of an agent (a) to the keratinous material, wherein         the agent (a) contains at least one organic silicon compound         selected from silanes having one, two or three silicon atoms,         wherein the organic silicon compound includes one or more         hydroxyl groups and/or hydrolysable groups per molecule, and         wherein the agent (a) further contains at least one         oligoalkylsiloxane, and     -   Application of an agent (b) to the keratinous material, the         agent (b) containing at least one coloring compound from the         group of pigments and/or direct dyes, the two agents (a) and (b)         being different from one another.

Agent (a)

As a first ingredient essential to the present disclosure, the composition (a) contains at least one organic silicon compound selected from silanes having one, two or three silicon atoms, the organic silicon compound including one or more hydroxyl groups and/or hydrolysable groups per molecule.

As already described, the organic silicon compounds or organic silanes contained in agent (a) are reactive compounds.

Composition (a) contains the organic silicon compound(s), in particular the organic silane(s), in a cosmetic carrier which may be hydrated, low in water or anhydrous. In addition, the cosmetic carrier can be liquid, gel-like, creamy, powdery, or even solid (e.g., in the form of a tablet or pellet). Suitably, the cosmetic carrier of the product (a) is an aqueous or aqueous-alcoholic carrier. To hair coloration, such carriers are, for example, creams, emulsions, gels, or surfactant-containing foaming solutions, such as shampoos, foam aerosols, foam formulations or other preparations suitable for application to the hair.

The cosmetic carrier suitably contains water, which means that the carrier contains at least about 2% by weight of water based on its weight. Suitably, the water content is above about 5 wt. %, further suitably above about 10 wt. % still further suitably above about 15 wt. %. The cosmetic carrier can also be aqueous-alcoholic. Aqueous/alcoholic solutions in the context of the present disclosure are aqueous solutions containing from about 2 to about 70% by weight of a C i-C₄ alcohol, more particularly ethanol or isopropanol. The agents as contemplated herein may additionally contain other organic solvents, such as methoxy butanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Exemplary are all water-soluble organic solvents.

The term “dyeing agent” is used in the context of this present disclosure for a coloration of the keratin material, of the hair, caused using pigments and/or direct dyes. In this staining process, the colorant compounds are deposited in a particularly homogeneous and smooth film on the surface of the keratin material or diffuse into the keratin fiber. The film is formed in situ by oligomerization or polymerization of the organic silicon compound(s), as well as by the interaction of organic silicon compound with the colorant compound.

Organic Silicon Compounds

As the first ingredient essential to the present disclosure, the agent (a) contains at least one organic silicon compound. Organic silicon compounds as contemplated herein are selected from silanes with one, two or three silicon atoms.

Organic silicon compounds, alternatively called organosilicon compounds, are compounds which either have a direct silicon-carbon bond (Si—C) or in which the carbon is bonded to the silicon atom via an oxygen, nitrogen, or sulfur atom. The organic silicon compounds as contemplated herein are compounds containing one to three silicon atoms. Organic silicon compounds suitably contain one or two silicon atoms.

According to IUPAC rules, the term silane chemical compounds based on a silicon skeleton and hydrogen. In organic silanes, the hydrogen atoms are completely or partially replaced by organic groups such as (substituted) alkyl groups and/or alkoxy groups. In organic silanes, some of the hydrogen atoms may also be replaced by hydroxy groups.

The agent (a) contains at least one organic silicon compound selected from silanes having one, two or three silicon atoms, wherein the organic silicon compound includes one or more hydroxyl groups or hydrolysable groups per molecule.

In a suitable embodiment, a method as contemplated herein is exemplified by the application of an agent (a) to the keratinous material, said agent (a) including at least one organic silicon compound selected from silanes having one, two or three silicon atoms, said organic silicon compound further including one or more basic chemical functions and one or more hydroxyl groups or hydrolysable groups per molecule.

This basic group can be, for example, an amino group, an alkylamino group or a dialkylamino group, which is suitably connected to a silicon atom via a linker. The basic group is suitably an amino group, a C₁-C₆ alkylamino group or a di(C₁-C₆)alkylamino group.

The hydrolysable group(s) is (are) suitably a C₁-C₆ alkoxy group, especially an ethoxy group or a methoxy group. It is exemplary when the hydrolysable group is directly bonded to the silicon atom. For example, if the hydrolysable group is an ethoxy group, the organic silicon compound suitably contains a structural unit R′R″R′″Si—O-CH2-CH3. The residues R′, R″ and R′″ represent the three remaining free valences of the silicon atom.

A suitable method as contemplated herein the composition includes (a) at least one organic silicon compound selected from silanes having one, two or three silicon atoms, the organic silicon compound suitably including one or more basic chemical functions and one or more hydroxyl groups or hydrolysable groups per molecule.

Particularly good results could be obtained if the agent as contemplated herein (a) contains at least one organic silicon compound of formula (I) and/or (II).

The compounds of formulae (I) and (II) are organic silicon compounds selected from silanes having one, two or three silicon atoms, the organic silicon compound including one or more hydroxyl groups and/or hydrolysable groups per molecule.

In another very suitable embodiment, a process as contemplated herein an agent (a) is applied to the keratinous material (or human hair), the agent (a) including at least one organic silicon compound (a) of the formula (I) and/or (II),

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

where

-   -   R₁, R₂ independently represent a hydrogen atom or a C₁-C₆ alkyl         group,     -   L is a linear or branched divalent C₁-C₂₀ alkylene group,     -   R₃ represents a hydrogen atom or a C₁-C₆ alkyl group,     -   R₄ represents a C₁-C₆ alkyl group     -   a, stands for an integer from 1 to 3, and     -   b stands for the integer 3-a,

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

-   -   R₅, R₅′, R₅″ independently represent a hydrogen atom or a C₁-C₆         alkyl group,     -   R₆, R₆′ and R₆″ independently represent a C₁-C₆ alkyl group,     -   A, A′, A″, A′″ and A″″ independently of one another represent a         linear or branched divalent C₁-C₂₀ alkylene group     -   R₇ and R₈ independently represent a hydrogen atom, a C₁-C₆ alkyl         group, a hydroxy C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, an         amino C₁-C₆ alkyl group or a group of formula (III)

-(A″″)-Si(R₆″)_(d)″(OR₅″)_(c)″  (III),

-   -   c, stands for an integer from 1 to 3,     -   d stands for the integer 3-c,     -   c′ stands for an integer from 1 to 3,     -   d′ stands for the integer 3-c′,     -   c″ stands for an integer from 1 to 3,     -   d″ stands for the integer 3-c″,     -   e stands for 0 or 1,     -   f stands for 0 or 1,     -   g stands for 0 or 1,     -   h stands for 0 or 1,     -   provided that at least one of e, f, g, and h is different from         0.

The substituents R₁, R₂, R₃, R₄, R₅, R₅′, R₅″, R₆, R₆′, R₆″, R₇, R₈, L, A, A′, A″, A″″ and A″″ in the compounds of formula (I) and (II) are explained below as examples: Examples of a C₁-C₆ alkyl group are the groups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, and t-butyl, n-pentyl and n-hexyl. Propyl, ethyl, and methyl are exemplary alkyl radicals. Examples of a C₂-C₆ alkenyl group are vinyl, allyl, but-2-enyl, but-3-enyl and isobutenyl, exemplary C₂-C₆ alkenyl radicals are vinyl and allyl. Exemplary examples of a hydroxy C₁-C₆ alkyl group are a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a 6-hydroxyhexyl group; a 2-hydroxyethyl group is suitable. Examples of an amino C₁-C₆ alkyl group are the aminomethyl group, the 2-aminoethyl group, the 3-aminopropyl group. The 2-aminoethyl group is suitable. Examples of a linear divalent C₁-C₂₀ alkylene group include the methylene group (—CH₂), the ethylene group (—CH₂—CH₂—), the propylene group (—CH₂—CH₂—CH₂—) and the butylene group (—CH₂—CH₂—CH₂—CH₂). The propylene group (—CH₂—CH₂—CH₂—) is suitable. From a chain length of 3 C atoms, divalent alkylene groups can also be branched. Examples of branched divalent C₃-C₂₀ alkylene groups are (—CH₂—CH(CH₃)—) and (—CH₂—CH(CH₃)—CH₂—).

In the organic silicon compounds of the formula (I)

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

the radicals R₁ and R₂ independently of one another represent a hydrogen atom or a C₁-C₆ alkyl group. In particular, the radicals R₁ and R₂ both represent a hydrogen atom.

In the middle part of the organic silicon compound is the structural unit or the linker -L- which stands for a linear or branched, divalent C₁-C₂₀ alkylene group.

Suitably -L- stands for a linear, divalent C₁-C₂₀ alkylene group. Further suitably -L-stands for a linear divalent C₁-C₆ alkylene group. Suitable -L- stands for a methylene group (—CH₂—), an ethylene group (—CH₂—CH₂—), propylene group (—CH₂—CH₂—CH₂—) or butylene (—CH₂—CH₂—CH₂—CH₂—). L stands for a propylene group (—CH₂—CH₂—CH₂—)

The organic silicon compounds of formula (I)

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

one end of each carries the silicon-containing group —Si(OR₃)_(a)(R₄)_(b)

In the terminal structural unit—Si(OR₃)_(a)(R₄)_(b), R₃ is hydrogen or C₁-C₆ alkyl group, and R₄ is C₁-C₆ alkyl group. R₃ and R₄ independently of each other represent a methyl group or an ethyl group.

Here a stands for an integer from 1 to 3, and b stands for the integer 3-a. If a stands for the number 3, then b is equal to 0. If a stands for the number 2, then b is equal to 1. If a stands for the number 1, then b is equal to 2.

Dyes with the best wash fastness values could be obtained if the pretreatment agent contains at least one organic silicon compound corresponding to formula (I): in which R₃, R₄ independently of one another represent a methyl group or an ethyl group.

Furthermore, dyeing's with the best wash fastness properties could be obtained if the agent as contemplated herein contains at least one organic silicon compound of formula (I) in which the radical a represents the number 3. In this case the rest b stands for the number 0.

In another exemplary embodiment, an agent as contemplated herein contains (a) at least one organic silicon compound of formula (I),

where

-   -   R₃, R₄ independently of one another represent a methyl group or         an ethyl group and     -   a stands for the number 3 and     -   b stands for the number 0.

In another exemplary embodiment, a process as contemplated herein the agent (a) contains at least one organic silicon compound of formula (I),

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

where

-   -   R₁, R₂ both represent a hydrogen atom, and     -   L represents a linear, divalent C₁-C₆-alkylene group, suitably a         propylene group (—CH₂—CH₂—CH₂—) or an ethylene group         (—CH₂—CH₂—),     -   R₃ represents a hydrogen atom, an ethyl group, or a methyl         group,     -   R₄ represents a methyl group or an ethyl group,     -   a stands for the number 3 and     -   b stands for the number 0.

Organic silicon compounds of the formula (I) which are particularly suitable for solving the problem as contemplated herein are.

In a further exemplary embodiment, a process as contemplated herein the agent (a) includes at least one organic silicon compound of formula (I) selected from the group including

-   (3-Aminopropyl)triethoxysilan -   (3-Aminopropyl)trimethoxysilane -   1-(3-Aminopropyl)silantriol -   (2-Aminoethyl)triethoxysilan -   (2-Aminoethyl)trimethoxysilane -   1-(2-Aminoethyl)silantriol -   (3-Dimethylaminopropyl)triethoxysilan -   (3-Dimethylaminopropyl)trimethoxysilane -   1-(3-Dimethylaminopropyl)silantriol -   (2-Dimethylaminoethyl)triethoxysilan. -   (2-Dimethylaminoethyl)trimethoxysilane and/or -   1-(2-Dimethylaminoethyl)silantriol.

The organic silicon compound of formula (I) is commercially available. (3-aminopropyl)trimethoxysilane, for example, can be purchased from Sigma-Aldrich. Also (3-aminopropyl)triethoxysilane is commercially available from Sigma-Aldrich.

In a further version, the present disclosure contains at least one organic silicon compound of formula (II)

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II).

The organosilicon compounds of formula (II) as contemplated herein each carry the silicon-containing groups (R₅O)_(c)(R₆)_(d)Si— and —Si(R₆′)_(d′)(OR₅′)_(c′) at both ends.

In the central part of the molecule of formula (II) there are the groups -(A)_(e)- and —[NR₇-(A′)]_(f)-

and [O-(A″)]_(g)- and —[NR₈-(A′″)]_(h)-. Here, each of the radicals e, f, g, and h can independently of one another stand for the number 0 or 1, with the proviso that at least one of the radicals e, f, g, and h is different from 0. In other words, an organic silicon compound of formula (II) as contemplated herein contains at least one grouping from the group including -(A)- and —[NR₇-(A′)]- and —[O-(A″)]- and —[NR₈-(A′″)]-.

In the two terminal structural units (R₅O)_(c)(R₆)_(d)Si— and —Si(R₆′)_(d′)(OR₅′)_(c′), the radicals R5, R5′, R5″ independently of one another represent a hydrogen atom or a C₁-C₆ alkyl group. The radicals R6, R6′ and R6″ independently represent a C₁-C₆ alkyl group.

Here a stands for an integer from 1 to 3, and d stands for the integer 3-c. If c stands for the number 3, then d is equal to 0. If c stands for the number 2, then d is equal to 1. If c stands for the number 1, then d is equal to 2.

Analogously c′ stands for a whole number from 1 to 3, and d′ stands for the whole number 3-c′. If c′ stands for the number 3, then d′ is 0. If c′ stands for the number 2, then d′ is 1. If c′ stands for the number 1, then d′ is 2.

Dyeing's with the best wash fastness values could be obtained if the residues c and c′ both stand for the number 3. In this case d and d′ both stand for the number 0.

In another exemplary embodiment, a process as contemplated herein the agent (a) contains at least one organic silicon compound of formula (II),

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

-   -   R5 and R5′ independently represent a methyl group or an ethyl         group,     -   c and c′ both stand for the number 3 and     -   d and d′ both stand for the number 0.

If c and c′ are both the number 3 and d and d′ are both the number 0, the organic silicon compound of the present disclosure corresponds to formula (Ha)

(R₅O)₃Si-(A)_(e)-[NR₇-(A′)]_(f)[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(OR₅′)₃  (IIa).

The radicals e, f, g, and h can independently stand for the number 0 or 1, whereby at least one radical from e, f, g, and h is different from zero. The abbreviations e, f, g, and h thus define which of the groupings -(A)_(e)- and [NR₇-(A′)]_(f)- and —[O-(A″)]_(g) and —[NR₈-(A′″)]_(h)-are in the middle part of the organic silicon compound of formula (II).

In this context, the presence of certain groupings has proved to be particularly beneficial in terms of increasing washability. Particularly good results were obtained when at least two of the residues e, f, g, and h stand for the number 1. Especially exemplary e and f both stand for the number 1. Furthermore, g and h both stand for the number 0.

If e and f both stand for the number 1 and g and h both stand for the number 0, the organic silicon compound as contemplated herein corresponds to formula (IIb)

(R₅O)_(c)(R₆)_(d)Si-(A)-[NR₇-(A′)]-Si(R₆′)_(d′)(OR₅′)_(c′)  (IIb).

The radicals A, A′, A″, A′″ and A″″ independently represent a linear or branched divalent C₁-C₂₀ alkylene group. Suitably the radicals A, A′, A″, A′″ and A″″ independently of one another represent a linear, divalent C₁-C₂₀ alkylene group. Further suitably the radicals A, A′, A″, A′″ and A″″ independently represent a linear divalent C₁-C₆ alkylene group. In particular, the radicals A, A′, A″, A′″ and A″″ independently of one another represent a methylene group (—CH₂—), an ethylene group (—CH₂—CH₂—), a propylene group (—CH₂—CH₂—CH₂—) or a butylene group (—CH₂—CH₂—CH₂—CH₂—). In particular, the residues A, A′, A″, A′″ and A″″ stand for a propylene group (—CH₂—CH₂—CH₂—).

If the radical f represents the number 1, then the organic silicon compound of formula (II) as contemplated herein contains a structural grouping —[NR₇-(A′)]-.

If the radical f represents the number 1, then the organic silicon compound of formula (II) as contemplated herein contains a structural grouping —[NR₈-(A′″)]-.

Wherein R₇ and R₈ independently represent a hydrogen atom, a C₁-C₆ alkyl group, a hydroxy-C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, an amino-C₁-C₆ alkyl group or a group of the formula (III)

-(A″″)-Si(R₆″)_(d)″(OR₅″)_(c)″  (III).

Very suitably the radicals R7 and R8 independently of one another represent a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a grouping of the formula (III).

If the radical f represents the number 1 and the radical h represents the number 0, the organic silicon compound as contemplated herein contains the grouping [NR₇-(A′)] but not the grouping —[NR₈-(A′″)]. If the radical R7 now stands for a grouping of the formula (III), the pretreatment agent (a) contains an organic silicon compound with 3 reactive silane groups.

In another exemplary embodiment, a process as contemplated herein the agent (a) contains at least one organic silicon compound of formula (II),

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

-   -   e and f both stand for the number 1,     -   g and h both stand for the number 0,     -   A and A′ independently represent a linear, divalent C₁-C₆         alkylene group         and     -   R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl         group, a 2-alkenyl group, a 2-aminoethyl group or a group of         formula (III).

In a further exemplary embodiment, a process as contemplated herein the agent (a) contains at least one organic silicon compound of the formula (II), where

-   -   e and f both stand for the number 1,     -   g and h both stand for the number 0,     -   A and A′ independently of one another represent a methylene         group (—CH₂—), an ethylene group (—CH₂—CH₂—) or a propylene         group (—CH₂—CH₂—CH₂), and     -   R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl         group, a 2-alkenyl group, a 2-aminoethyl group or a group of         formula (III).

Organic silicon compounds of the formula (II) which are well suited for solving the problem as contemplated herein are.

The organic silicon compounds of formula (II) are commercially available.

Bis(trimethoxysilylpropyl)amines with the CAS number 82985-35-1 can be purchased from Sigma-Aldrich. Bis[3-(triethoxysilyl)propyl]amines with the CAS number 13497-18-2 can be purchased from Sigma-Aldrich, for example. N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine is alternatively referred to as bis(3-trimethoxysilylpropyl)-N-methylamine and can be purchased commercially from Sigma-Aldrich or Fluorochem. 3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine with the CAS number 18784-74-2 can be purchased for example from Fluorochem or Sigma-Aldrich.

In another exemplary embodiment, an agent as contemplated herein contains (a) at least one organic silicon compound of formula (II) selected from the group including

-   3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine -   3-(Triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine -   N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine -   N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine -   2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol -   2-[bis[3-(triethoxysilyl)propyl]amino]ethanol -   3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine -   3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine -   N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine, -   N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine, -   N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine and/or -   N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine

In further dyeing tests, it has also proved to be particularly advantageous if the agent used on the keratinous material in the process as contemplated herein (a) contains at least one organic silicon compound of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV).

The compounds of formula (IV) are organic silicon compounds selected from silanes having one, two or three silicon atoms, the organic silicon compound including one or more hydroxyl groups and/or hydrolysable groups per molecule.

The organic silicon compound(s) of formula (IV) may also be called a silane of the alkyl-alkoxy-silane or alkyl-hydroxy-silane type,

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

-   -   R₉ represents a C₁-C₁₂, alkyl group,     -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,     -   R₁₁ represents a C₁-C₆ alkyl group     -   k is an integer from 1 to 3, and     -   m stands for the integer 3-k.

In another exemplary embodiment, a process as contemplated herein the agent (a) contains at least one organic silicon compound of formula (IV).

R₉Si(OR₁₀)k(R₁₁)_(m)  (IV),

where

-   -   R₉ represents a C₁-C₁₂ alkyl group,     -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,     -   R₁₁ represents a C₁-C₆ alkyl group     -   k is an integer from 1 to 3, and     -   m stands for the integer 3-k.

In a further exemplary embodiment, a process as contemplated herein the agent (a) contains, in addition to the organic silicon compound(s) of formula (I), at least one further organic silicon compound of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

-   -   R₉ represents a C₁-C₁₂ alkyl group,     -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,     -   R₁₁ represents a C₁-C₆ alkyl group     -   k is an integer from 1 to 3, and     -   m stands for the integer 3-k.

In a further exemplary embodiment, a process as contemplated herein the agent (a) contains, in addition to the organic silicon compound or compounds of the formula (II), at least one further organic silicon compound of the formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

-   -   R₉ represents a C₁-C₁₂ alkyl group,     -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,     -   R₁₁ represents a C₁-C₆ alkyl group     -   k is an integer from 1 to 3, and     -   m stands for the integer 3-k.

In a further exemplary embodiment, a process as contemplated herein the composition contains (a) in addition to the organic silicon compound(s) of formula (I) and/or (II) at least one further organic silicon compound of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

-   -   R₉ represents a C₁-C₁₂ alkyl group,     -   R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,     -   R₁₁ represents a C₁-C₆ alkyl group     -   k is an integer from 1 to 3, and     -   m stands for the integer 3-k.

In the organic silicon compounds of formula (IV), the radical R₉ represents a C₁-C₁₂ alkyl group. This C₁-C₁₂ alkyl group is saturated and can be linear or branched. Suitably R9 stands for a linear C₁-C₈ alkyl group. Suitably R₉ stands for a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group or an n-dodecyl group. Suitable, R₉ stands for a methyl group, an ethyl group or an n-octyl group.

In the organic silicon compounds of formula (IV), the radical R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group. R10 stands for a methyl group or an ethyl group.

In the organic silicon compounds of formula (IV), the radical R₁₁ represents a C₁-C₆ alkyl group. R11 stands for a methyl group or an ethyl group.

Furthermore, k stands for a whole number from 1 to 3, and m stands for the whole number 3-k. If k stands for the number 3, then m is equal to 0. If k stands for the number 2, then m is equal to 1. If k stands for the number 1, then m is equal to 2.

Dyes with the best wash fastness values could be obtained if an agent (a) were used in the process which contains at least one organic silicon compound of the formula (IV) in which the radical k stands for the number 3. In this case the rest m stands for the number 0.

Organic silicon compounds of the formula (IV) which are particularly suitable for solving the problem as contemplated herein are.

In another exemplary embodiment, a process as contemplated herein the agent (a) contains at least one organic silicon compound of formula (IV) selected from the group including

-   -   Methyltrimethoxysilane     -   Methyltriethoxysilane     -   Ethyltrimethoxysilane     -   Ethyltriethoxysilane     -   Hexyltrimethoxysilane     -   Hexyltriethoxysilane     -   Octyltrimethoxysilane     -   Octyltriethoxysilane     -   Dodecyltrimethoxysilane and/or     -   Dodecyltriethoxysilane.

In an explicitly suitable embodiment, a process as contemplated herein an agent (a) is applied to the keratinous material which contains at least one organic silicon compound of the formula (I) which is selected from the group including (3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane, and additionally contains at least one organic silicone compound of formula (IV) selected from the group including methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane.

The organic silicon compounds described above are reactive compounds. In this context, it has been found to be exemplary if the agent (a) of the present disclosure—based on the total weight of agent (a)—contains one or more organic silicon compounds in a total amount of from about 0.1 to about 20.0% by weight, suitably from about 1.0 to about 15.0% by weight and particularly suitably from about 2.0 to about 8.0% by weight.

In a further exemplary embodiment, a process as contemplated herein the agent (a)—based on the total weight of agent (a)—contains one or more organic silicon compounds in a total amount of from about 0.1 to about 20.0% by weight, suitably from about 1.0 to about 15.0% by weight and particularly suitably from about 2.0 to about 8.0% by weight.

To achieve particularly good dyeing results, it is particularly advantageous to use the organic silicon compounds of the formula (I) and/or (II) in certain quantity ranges on average (a). Particularly suitably, the agent (a) contains—based on the total weight of the agent (a)—one or more organic silicon compounds of the formula (I) and/or (II) in a total amount of from about 0.1 to about 10.0% by weight, suitably from about 0.5 to about 5.0% by weight and particularly suitably from about 1.0 to about 3.0% by weight.

In a further exemplary embodiment, a process as contemplated herein the agent (a) contains—based on the total weight of the agent (a)—one or more organic silicon compounds of the formula (I) and/or (II) in a total amount of from about 0.1 to about 10.0% by weight, suitably from about 0.5 to about 5.0% by weight and particularly suitably from about 1.0 to about 3.0% by weight.

Furthermore, it has proven to be suitable if the organic silicon compound(s) of formula (IV) is (are) also present in certain quantity ranges in average (a). Particularly suitably the agent (a) contains—based on the total weight of agent (a)—one or more organic silicon compounds of the formula (IV) in a total amount of from about 0.1 to about 20.0% by weight, suitably from about 2.0 to about 15.0% by weight and particularly suitably from about 4.0 to about 9.0% by weight.

In a further exemplary embodiment, a process as contemplated herein the agent (a) contains—based on the total weight of the agent (a)—one or more organic silicon compounds of the formula (IV) in a total amount of from about 0.1 to about 20.0% by weight, suitably from about 2.0 to about 15.0% by weight and particularly suitably from about 4.0 to about 9.0% by weight.

Oligoalkylsiloxanes

As a second constituent essential to the present disclosure, the composition (a) contains at least one oligoalkylsiloxane.

For the purposes of the present disclosure, oligoalkylsiloxanes are understood to be oligomeric siloxanes, which may be linear or cyclic.

Exemplary linear oligoalkylsiloxanes are compounds of the general formula (V)

where z is an integer from 0 to 10. Suitably, z stands for the numbers 0, 1, 2 or 3.

Very suitable linear oligoalkylsiloxanes are for example.

Hexamethyldisiloxane has the CAS number 107-46-0 and can be purchased commercially from Sigma-Aldrich, for example.

Octamethyltrisiloxane has the CAS number 107-51-7 and is also commercially available from Sigma-Aldrich. Decamethyltetrasiloxane carries the CAS number 141-62-8 and is also commercially available from Sigma-Aldrich. Exemplary cyclic oligoalkylsiloxanes are compounds of the general formula (VI)

where y is an integer from 1 to 5. Suitably, z stands for the numbers 1, 2 or 3.

Very suitable cyclic oligoalkylsiloxanes include.

-   -   Hexamethylcyclotrisiloxane     -   Octamethylcyclotetrasiloxane     -   Decamethylcyclopentasiloxane

In a further exemplary embodiment, a method as contemplated herein the agent (a) includes at least one linear and/or cyclic oligoalkylsiloxane.

In a further exemplary embodiment, a method as contemplated herein the composition (a) includes at least one oligoalkylsiloxane of the formula (V) and/or (VI),

where z is an integer from 0 to 10, suitably an integer from 0 to 3,

where y is an integer from 1 to 5, suitably an integer from 1 to 3.

In a further exemplary embodiment, a method as contemplated herein the composition (a) includes at least one oligoalkylsiloxane selected from the group including hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and/or decamethylcyclopentasiloxane.

In contrast to the reactive organic silicon compounds, i.e., the silanes of formulae (I), (II) and (IV), the oligoalkylsiloxanes are composed exclusively of dialkylsilyl groups (dimethylsilyl groups) and trialkylsilyl groups (trimethylsilyl groups), which are linked to one another via oxygen atoms. Thus, the oligoalkylsiloxanes themselves are not reactive compounds and do not possess hydrolysable groups.

It was found that the agents (a), which in addition to the organic silicon compounds (silanes) also contained oligoalkylsiloxanes, had particularly good storage stability. Without being limited to this theory, it is believed that the reactive organic silicic compounds (especially the silane formulas (I), (II), and (IV)) dissolve very well in the oligoalkylsiloxanes, with the inert character of the oligoalkylsiloxanes preventing the silanes from reacting too quickly and protecting the silanes from atmospheric moisture. In this way, the silanes contained in agent (a) did not react prematurely in an undesirable manner, and their reactivity was preserved.

When used in the dyeing process, it was shown that a consistently good color result could be achieved in this way, regardless of the conditions prevailing during dyeing. Stains applied at high humidity were as good as those applied at lower humidity.

Therefore, it was also possible to achieve a particularly high color intensity when using agent (a) in the process as contemplated herein, since a particularly homogeneous film was formed on the keratin material when agent (a) was applied, which still had enough reactive sites to bind the direct dyes of agent (b).

This effect could be achieved when the agent (a) contained the oligoalkylsiloxane(s) in certain amount ranges. It has been found to be suitable if the agent (a)—based on the total weight of the agent (a)—contains one or more oligoalkylsiloxanes in a total amount of from about 0.1 to about 25.0% by weight, suitably from about 1.0 to about 15.0% by weight-5, more suitably from about 1.5 to about 10.0% by weight and very particularly suitably from about 2.0 to about 9.0% by weight.

In a further exemplary embodiment, a process as contemplated herein the agent (a) contains—based on the total weight of the agent (a)—one or more oligoalkylsiloxanes in a total amount of from about 0.1 to about 25.0% by weight, suitably from about 1.0 to about 15.0% by weight-5, more suitably from about 1.5 to about 10.0% by weight and very particularly suitably from about 2.0 to about 9.0% by weight.

For optimum control of the rate of polymerization of the silanes, it has further been found to be particularly advantageous to use the organic silicon compounds and the oligoalkylsilxoans in specific proportions in the medium (a).

In a further exemplary embodiment, a process as contemplated herein the weight ratio of all organic silicon compounds of the formulae (I), (II) and (IV) contained in the agent (a) to all oligoalkylsiloxanes of the formulae (V) and (VI) contained in the agent (a) is from about 5:1 to about 1:1, suitably from about 3:1 to about 1:1 and particularly suitably from about 2:1 to about 1:1.

Example: An agent (a) contains:

-   -   about 2.0% by weight 3-aminopropyltriethoxysilane and     -   about 7.0 wt. % methyltrimethoxsilane and     -   about 5.0 wt. % hexamethyldisiloxane         The weight ratio of all organic silicon compounds of formulae         (I), (II) and (IV) contained in the medium (a) to all         oligoalkylsiloxanes of formulae (V) and (VI) contained in the         medium (a) is (2.0+7.0)/5.0=1.8

Particularly resistant strains could be obtained when using an alkaline adjusted agent (a). Suitably, agent (a) contains water and has a pH of from about 7.0 to about 11.5, suitably from about 7.5 to about 11.0, and more suitably from about 8.0 to about 10.5.

In another very suitable embodiment, a process as contemplated herein the agent (a) has a pH of from about 7.0 to about 11.5, suitably from about 7.5 to about 11.0 and particularly suitably from about 8.0 to about 10.5.

Agent (b)

The agent (b) is exemplified by its content of at least one pigment and/or a direct dye. The agent (b) may also be called colorant (b).

Pigments within the meaning of the present disclosure are coloring compounds which have a solubility in water at about 25° C. of less than about 0.5 g/L, suitably less than about 0.1 g/L, even more suitably less than about 0.05 g/L. Water solubility can be determined, for example, by the method described below: about 0.5 g of the pigment are weighed in a beaker. A stir-fish is added. Then one liter of distilled water is added. This mixture is heated to about 25° C. for one hour while stirring on a magnetic stirrer. If undissolved components of the pigment are still visible in the mixture after this period, the solubility of the pigment is below about 0.5 g/L. If the pigment-water mixture cannot be assessed visually due to the high intensity of the possibly finely dispersed pigment, the mixture is filtered. If a proportion of undissolved pigments remains on the filter paper, the solubility of the pigment is below about 0.5 g/L.

Suitable color pigments can be of inorganic and/or organic origin.

In a exemplary embodiment, an agent (b) of the present disclosure contains at least one colorant compound from the group of inorganic and/or organic pigments.

Exemplary color pigments are selected from synthetic or natural inorganic pigments. Inorganic color pigments of natural origin can be produced, for example, from chalk, ochre, umber, green earth, burnt Terra di Siena or graphite. Furthermore, black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red as well as fluorescent or phosphorescent pigments can be used as inorganic color pigments.

Particularly suitable are colored metal oxides, hydroxides and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, silicates, metal sulphides, complex metal cyanides, metal sulphates, chromates and/or molybdates. Exemplary color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfo silicates, CI 77007, pigment blue 29), chromium oxide hydrate (CI77289), iron blue (ferric ferrocyanides, CI77510) and/or carmine (cochineal).

As contemplated herein, colored pearlescent pigments are also suitable color pigments. These are usually mica- and/or mica-based and can be coated with one or more metal oxides. Mica belongs to the layer silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce the pearlescent pigments in combination with metal oxides, the mica, mainly muscovite or phlogopite, is coated with a metal oxide.

As an alternative to natural mica, synthetic mica coated with one or more metal oxides can also be used as pearlescent pigment. Especially exemplary pearlescent pigments are based on natural or synthetic mica (mica) and are coated with one or more of the metal oxides mentioned above. The color of the respective pigments can be varied by varying the layer thickness of the metal oxide(s).

In a further exemplary embodiment, a process as contemplated herein the agent (b) contains at least one colorant compound from the group of pigments selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, complex metal cyanides, metal sulfates, bronze pigments and/or from colored pigments based on mica or mica which are coated with at least one metal oxide and/or one metal oxychloride.

In a further exemplary embodiment, an agent as contemplated herein contains (b) at least one colorant compound from the group of pigments selected from pigments based on mica or micaceous iron oxide, which is combined with one or more metal oxides from the group of titanium dioxide (CI 77891), are coated with black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and/or brown iron oxide (CI 77491, CI 77499), manganese violet (CI 77742), ultramarine (sodium aluminum sulfo silicates, CI 77007, pigment blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288) and/or iron blue (ferric ferrocyanides, CI 77510).

Examples of particularly suitable color pigments are commercially available under the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® from Eckart Cosmetic Colors and Sunshine® from Sunstar.

Suitable color pigments with the trade name Colorona® are, for example:

Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides), Alumina Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470 (CARMINE) Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC FERROCYANIDE Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE) Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360) Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 77288 (CHROMIUM OXIDE GREENS) Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510) Colorona Red Gold, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRON OXIDES (CI 77491) Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES) Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze Fine, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Fine Gold MP 20, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Sienna Fine, Merck, CI 77491 (IRON OXIDES), MICA Colorona Sienna, Merck, MICA, CI 77491 (IRON OXIDES)

Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide), Silica, CI 77491 (Iron oxides), Tin oxide

Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRON OXIDES, MICA, CI 77891, CI 77491 (EU)

Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891 (Titanium dioxide) Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491 (Iron oxides)

Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

Other suitable color pigments with the trade name Xirona® are for example:

Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica, Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin Oxide.

In addition, suitable color pigments with the trade name Unipure® are for example:

Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

In a further embodiment, the means as contemplated herein may also contain (b) one or more coloring compounds from the group of organic pigments.

The organic pigments as contemplated herein are correspondingly insoluble, organic dyes or color lacquers, which may be selected, for example, from the group of nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindolinone, quinacridone, perinone, perylene, diketo-pyrrolopyorrole, indigo, thioindido, dioxazine and/or triarylmethane compounds.

Examples of particularly suitable organic pigments are carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the Color Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the Color Index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with the Color Index numbers CI 61565, CI 61570, CI 74260, orange pigments with the Color Index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

In a further suitable embodiment, a process as contemplated herein the agent (b) contains at least one colorant compound from the group of organic pigments selected from the group of carmine, quinacridone, phthalocyanine, sorghum, blue pigments with the Color Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments with the Color Index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with Color Index numbers CI 61565, CI 61570, CI 74260, orange pigments with Color Index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

The organic pigment can also be a color paint. As contemplated herein, the term color lacquer means particles including a layer of absorbed dyes, the unit of particle and dye being insoluble under the above-mentioned conditions. The particles can, for example, be inorganic substrates, which can be aluminum, silica, calcium borosilate, calcium aluminum borosilicate or even aluminum.

For example, alizarin color varnish can be used.

Due to their excellent light and temperature resistance, the use of the pigments in agent (b) of the process as contemplated herein is suitable. It is also exemplary if the pigments used have a certain particle size. As contemplated herein, it is therefore advantageous if the at least one pigment has an average particle size D₅₀ of from about 1.0 to about 50 μm, suitably from about 5.0 to about 45 μm, suitably from about 10 to about 40 μm, from about 14 to about 30 μm. The mean particle size D₅₀, for example, can be determined using dynamic light scattering (DLS).

The pigment or pigments may be used in an amount of from about 0.001 to about 20% by weight, of from about 0.05 to about 5% by weight, each based on the total weight of agent (b).

As colorant compounds, the agents (b) used in the process as contemplated herein may also contain one or more direct dyes. Direct-acting dyes are dyes that draw directly onto the hair and do not require an oxidative process to form the color. Direct dyes are usually nitro phenylene diamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes or indophenols.

The direct dyes within the meaning of the present disclosure have a solubility in water (760 mmHg) at about 25° C. of more than about 0.5 g/L and are therefore not to be regarded as pigments.

Suitably, the direct dyes within the meaning of the present disclosure have a solubility in water (760 mmHg) at about 25° C. of more than about 1.0 g/L.

Direct dyes can be divided into anionic, cationic, and non-ionic direct dyes.

In a further exemplary embodiment, an agent as contemplated herein contains as coloring compound (b) at least one anionic, cationic and/or non-ionic direct dye.

In a further exemplary embodiment, an agent as contemplated herein contains (b) at least one anionic, cationic and/or non-ionic direct dye.

Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26, Basic Violet 2, and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347/Dystar), HC Blue No. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow 87, Basic Orange 31, Basic Red 51 Basic Red 76

As non-ionic direct dyes, non-ionic nitro and quinone dyes and neutral azo dyes can be used. Suitable non-ionic direct dyes are those listed under the international designations or Trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-(2-hydroxyethyl)-aminophenol 2-(2-hydroxyethyl)amino-4,6-dinitrophenol, 4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene, 1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene, 2-[(4-amino-2-nitrophenyl)amino]benzoic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

In a further exemplary embodiment, a process as contemplated herein the agent (b) includes at least one direct dye selected from the group including anionic, cationic, and nonionic direct dyes.

In the course of the work leading to the present disclosure, it has been found that dyeing's of particularly high color intensity can be produced with agents (b) containing at least one anionic direct dye.

In an explicitly quite suitable embodiment, an agent (b) used in the process as contemplated herein contains at least one anionic direct dye.

Anionic direct dyes are also called acid dyes. Acid dyes are direct dyes that have at least one carboxylic acid group (—COOH) and/or one sulphonic acid group (—SO₃H). Depending on the pH value, the protonated forms (—COOH, —SO₃H) of the carboxylic acid or sulphonic acid groups are in equilibrium with their deprotonated forms (—COO⁻, —SO₃ ⁻ present). The proportion of protonated forms increases with decreasing pH value. If direct dyes are used in the form of their salts, the carboxylic acid groups or sulphonic acid groups are present in deprotonated form and are neutralized with corresponding stoichiometric equivalents of cations to maintain electro neutrality. Inventive acid dyes can also be used in the form of their sodium salts and/or their potassium salts.

The acid dyes within the meaning of the present disclosure have a solubility in water (760 mmHg) at about 25° C. of more than about 0.5 g/L and are therefore not to be regarded as pigments. Suitably the acid dyes within the meaning of the present disclosure have a solubility in water (760 mmHg) at about 25° C. of more than about 1.0 g/L.

The alkaline earth salts (such as calcium salts and magnesium salts) or aluminum salts of acid dyes often have a lower solubility than the corresponding alkali salts. If the solubility of these salts is below about 0.5 g/L (25° C., 760 mmHg), they do not fall under the definition of a direct dye.

An essential characteristic of acid dyes is their ability to form anionic charges, whereby the carboxylic acid or sulphonic acid groups responsible for this are usually linked to different chromophoric systems. Suitable chromophoric systems can be found, for example, in the structures of nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and/or indophenol dyes.

In one embodiment of the process, the use of an agent (b) which contains at least one anionic direct dye selected from the group including nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and/or indophenol dyes is thus exemplary, the rhodamine dyes, the oxazine dyes and/or the indophenol dyes, the dyes from the abovementioned group each having at least one carboxylic acid group (—COOH), a sodium carboxylate group (—COONa), a potassium carboxylate group (—COOK), a sulfonic acid group (—SO₃H), a sodium sulfonate group (—SO₃Na) and/or a potassium sulfonate group (—SO₃K).

For example, one or more compounds from the following group can be selected as particularly well suited acid dyes: Acid Yellow 1 (D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA no B001), Acid Yellow 3 (COLIPA n°: C 54, D&C Yellow No 10, Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965), Acid Yellow 23 (COLIPA no C. 29, Covacap Jaune W 1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA no C015), Acid Orange 10 (C.I. 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (BROWN 1; CI 20170; KATSU201; no sodium salt; Brown No. 201; RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201; D & C Brown No. 1), Acid Red 14 (C.I. 14720), Acid Red 18 (E124, Red 18; CI 16255), Acid Red 27 (E 123, CI 16185, C-Rot 46, Echtrot D, FD&C Red Nr. 2, Food Red 9, Naphtholrot S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, CI 17200), Acid Red 35 (CI C.I. 18065), Acid Red 51 (CI 45430, Pyrosin B, Tetraiodfluorescein, Eosin J, Iodeosin), Acid Red 52 (CI 45100, Food Red 106, Solar Rhodamine B, Acid Rhodamine B, Red no 106 Pontacyl Brilliant Pink), Acid Red 73 (CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red 92 (COLIPA no C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine, Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43, Ext. D&C Violet no 2, C.I. 60730, COLIPA no C063), Acid Violet 49 (CI 42640), Acid Violet 50 (CI 50325), Acid Blue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent Blue V, CI 42051), Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blue 9 (E 133, Patent blue AE, Amidoblau AE, Erioglaucin A, CI 42090, C.I. Food Blue 2), Acid Blue 62 (CI 62045), Acid Blue 74 (E 132, CI 73015), Acid Blue 80 (CI 61585), Acid Green 3 (CI 42085, Foodgreen1), Acid Green 5 (CI 42095), Acid Green 9 (C.I. 42100), Acid Green 22 (C.I. 42170), Acid Green 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50 (Brilliant Acid Green BS, C.I. 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black no 401, Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA no B15), Acid Black 52 (CI 15711), Food Yellow 8 (CI 14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and/or D&C Brown 1.

The water solubility of direct dyes can be determined, for example, in the following way. about 0.1 g of the anionic dye is added to a beaker. A stir-fish is added. Then add about 100 ml of water. This mixture is heated to about 25° C. on a magnetic stirrer while stirring. It is stirred for about 60 minutes. The aqueous mixture is then visually assessed. If there are still undissolved residues, the amount of water is increased—for example in steps of 10 ml. Water is added until the amount of dye used is completely dissolved. If the dye-water mixture cannot be assessed visually due to the high intensity of the dye, the mixture is filtered. If a proportion of undissolved dyes remains on the filter paper, the solubility test is repeated with a higher quantity of water. If about 0.1 g of the anionic direct dye dissolves in about 100 ml water at 25° C., the solubility of the dye is about 1.0 g/L.

Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water of at least about 40 g/L (25° C.).

Acid Yellow 3 is a mixture of the sodium salts of mono- and sisulfonic acids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a water solubility of about 20 g/L (25° C.).

Acid Yellow 9 is the disodium salt of 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, its solubility in water is above about 40 g/L (25° C.). Acid Yellow 23 is the trisodium salt of 4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylic acid and is highly soluble in water at about 25° C. Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzene sulphonate. Its water solubility is more than about 7 g/L (25° C.). Acid Red 18 is the trinatirum salt of 7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalene disulfonate and has a very high-water solubility of more than about 20% by weight. Acid Red 33 is the diantrium salt of 5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulphonate, its solubility in water is about 2.5 g/L (25° C.). Acid Red 92 is the disodium salt of 3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoic acid, whose solubility in water is indicated as greater than about 10 g/L (25° C.). Acid Blue 9 is the disodium salt of 2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonate and has a solubility in water of more than about 20% by weight (25° C.).

A very suitable process as contemplated herein the agent (b) includes at least one anionic direct dye selected from the group including Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and/or D&C Brown 1.

The direct dye(s), in the anionic direct dyes, can be used in different amounts in the agent (b) depending on the desired color intensity. Particularly good results were obtained when the agent (b)—based on the total weight of the agent (b)—contains one or more direct dyes in a total amount of from about 0.01 to about 10.0% by weight, suitably from about 0.1 to about 8.0% by weight, more suitably from about 0.2 to about 6.0% by weight and most suitably from about 0.5 to about 4.5% by weight.

In a further exemplary embodiment, an agent (b) contains—based on the total weight of the agent (b)—one or more direct dyes in a total amount of from about 0.01 to about 10.0% by weight, suitably from about 0.1 to about 8.0% by weight, more suitably from about 0.2 to about 6.0% by weight and most suitably from about 0.5 to about 4.5% by weight.

In a further exemplary embodiment, an agent as contemplated herein contains—based on the total weight of the agent (b)—one or more anionic direct dyes (b) in a total amount of from about 0.01 to about 10.0% by weight, suitably from about 0.1 to about 8.0% by weight, more suitably from about 0.2 to about 6.0% by weight and very particularly suitably from about 0.5 to about 4.5% by weight.

Other Ingredients in Products (a) and (b)

The agents (a) and (b) described above may also contain one or more optional ingredients.

The products may also contain one or more surfactants. The term surfactants refer to surface-active substances. A distinction is made between anionic surfactants including a hydrophobic residue and a negatively charged hydrophilic head group, amphoteric surfactants, which carry both a negative and a compensating positive charge, cationic surfactants, which in addition to a hydrophobic residue have a positively charged hydrophilic group, and non-ionic surfactants, which have no charges but strong dipole moments and are strongly hydrated in aqueous solution.

Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one —COO⁽⁻⁾— or —SO₃ ⁽⁻⁾ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N,N-dimethylammonium-glycinate, for example the cocoalkyl-dimethylammoniumglycinate, N-acylaminopropyl-N,N-dimethylammoniumglycinate, for example, cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines each having 8 to 18 C atoms in the alkyl or acyl group, and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A exemplary zwitterionic surfactant is the fatty acid amide derivative known under the INCI name cocamidopropyl betaine.

Ampholytic surfactants are surface-active compounds which, apart from a C₈-C₂₄ alkyl or acyl group, contain at least one free amino group and at least one —COOH— or —SO₃H group in the molecule and can form internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 24 C atoms in the alkyl group. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, amino propionates, aminoglycinate, imidazoliniumbetaines and sulfobetaines.

Suitable ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C₁₂-C₁₈ acylsarcosine.

The products may also additionally contain at least one non-ionic surfactant. Suitable non-ionic surfactants are alkyl polyglycosides as well as alkylene oxide addition products to fatty alcohols and fatty acids with 2 to 30 mol ethylene oxide per mol fatty alcohol or fatty acid. Preparations with good properties are also obtained if they contain as non-ionic surfactants fatty acid esters of ethoxylated glycerol reacted with at least 2 mol ethylene oxide. The non-ionic surfactants are used in a total quantity of from about 0.1 to about 45% by weight, suitably from about 1 to about 30% by weight and very suitably from about 1 to about 15% by weight—based on the total weight of the respective agent.

In addition, the products may also contain at least one cationic surfactant. Cationic surfactants are surfactants, i.e., surface-active compounds, each with one or more positive charges. Cationic surfactants contain only positive charges. Usually, these surfactants are composed of a hydrophobic part and a hydrophilic head group, the hydrophobic part usually including a hydrocarbon backbone (e.g., including one or two linear or branched alkyl chains) and the positive charge(s) being in the hydrophilic head group. Examples of cationic surfactants are

-   -   quaternary ammonium compounds which, as hydrophobic radicals,         may carry one or two alkyl chains with a chain length of 8 to 28         C atoms,     -   quaternary phosphonium salts substituted with one or more alkyl         chains with a chain length of 8 to 28 C atoms or     -   tertiary sulfonium salts.

Furthermore, the cationic charge can also be part of a heterocyclic ring (e.g., an imidazolium ring or a pyridinium ring) in the form of an onium structure. In addition to the functional unit carrying the cationic charge, the cationic surfactant may also contain other uncharged functional groups, as is the case for example with esterquats. The cationic surfactants are used in a total quantity of from about 0.1 to about 45 wt. %, suitably from about 1 to about 30 wt. % and most suitably from about 1 to about 15 wt. %—based on the total weight of the respective agent.

Furthermore, the means as contemplated herein may also contain at least one anionic surfactant. Anionic surfactants are surface-active agents with exclusively anionic charges (neutralized by a corresponding counter cation). Examples of anionic surfactants are fatty acids, alkyl sulphates, alkyl ether sulphates and ether carboxylic acids with 12 to 20 C atoms in the alkyl group and up to 16 glycol ether groups in the molecule.

The anionic surfactants are used in a total quantity of from about 0.1 to about 45 wt. %, suitably from about 1 to about 30 wt. % and most suitably from about 1 to about 15 wt. % —based on the total weight of the respective agent.

To adjust the desired pH, agents (a), (b) and (c) may also contain at least one alkalizing agent and/or acidifying agent. The pH values for the purposes of the present disclosure are pH values measured at a temperature of about 22° C.

As alkalizing agents, agents (a), (b) and (c) may contain for example ammonia, alkanolamines and/or basic amino acids.

The alkanolamines which can be used in the composition of the present disclosure are suitably selected from primary amines having a C₂-C₆ alkyl base which carries at least one hydroxyl group. Exemplary alkanolamines are selected from the group formed by 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol.

Alkanolamines suitable as contemplated herein are selected from 2-aminoethan-1-ol and/or 2-amino-2-methylpropan-1-ol. A suitable embodiment the agent as contemplated herein contains an alkanolamine selected from 2-aminoethan-1-ol and/or 2-amino-2-methylpropan-1-ol as alkalizing agent.

A suitable embodiment the agent as contemplated herein contains an alkanolamine selected from 2-aminoethan-1-ol and/or 2-amino-2-methylpropan-1-ol as alkalizing agent. For the purposes of the present disclosure, an amino acid is an organic compound which in its structure contains at least one protonatable amino group and at least one —COOH or one —SO₃H group. Exemplary amino acids are aminocarboxylic acids, especially α-(alpha)-aminocarboxylic acids and ω-aminocarboxylic acids, whereby α-aminocarboxylic acids are suitable.

As contemplated herein, basic amino acids are those amino acids which have an isoelectric point pI of greater than about 7.0.

Basic α-aminocarboxylic acids contain at least one asymmetric carbon atom. In the context of the present disclosure, both possible enantiomers can be used equally as specific compounds or their mixtures, especially as racemates. However, it is particularly advantageous to use the naturally exemplary isomeric form, usually in L-configuration.

The basic amino acids are suitably selected from the group formed by arginine, lysine, ornithine, and histidine, especially suitably arginine and lysine. In another suitable embodiment, an agent as contemplated herein the alkalizing agent is a basic amino acid from the group arginine, lysine, ornithine and/or histidine.

In addition, the product may contain other alkalizing agents, especially inorganic alkalizing agents. Inorganic alkalizing agents usable as contemplated herein are suitably selected from the group formed by sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

Suitable alkalizing agents are ammonia, 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-Amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol, arginine, lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate and potassium carbonate.

Acidifiers commonly used by experts are, for example, indulgence acids such as citric acid, acetic acid, malic acid, or tartaric acid, as well as diluted mineral acids such as hydrochloric acid, sulfuric acid, or phosphoric acid.

They may also contain other active substances, auxiliaries and additives, such as solvents, fatty components such as C₈-C₃₀ fatty alcohols, C₈-C₃₀ fatty acid triglycerides, C₅-C₃₀ fatty acid monoglycerides, C₈-C₃₀ fatty acid diglycerides and/or hydrocarbons; polymers, structural agents such as glucose, maleic acid and lactic acid; hair conditioning compounds such as phospholipids, for example lecithin and cephalins; perfume oils, dimethylisosorbide and cyclodextrins; fiber structure-improving active substances, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose; dyes for coloring the composition; anti-dandruff active substances such as Piroctone Olamine, Zinc Omadine and Climbazol; amino acids and oligopeptides; protein hydrolysates on animal and/or vegetable basis, as well as in the form of their fatty acid condensation products or optionally anionic or cationically modified derivatives; vegetable oils; sunscreens and UV-blockers; active ingredients such as panthenol, pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts, and bisabolol; polyphenols, in particular hydroxycinnamic acids, 6,7-dihydroxycumarine, hydroxybenzoic acids, catechine, tannine, leukoanthocyanidine, anthocyanidine, flavanone, flavone and flavonols; ceramides or pseudoceramides; vitamins, provitamins and vitamin precursors; plant extracts; fats and waxes such as fatty alcohols, beeswax, montan wax and paraffins; swelling and penetrating substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates; opacifiers such as latex, styrene/PVP and styrene/acrylamide copolymers; pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate; and blowing agents such as propane-butane mixtures, N₂O, dimethyl ether, CO₂ and air.

Very particularly suitably, the composition (b) additionally includes at least one anionic polymer selected from the group including the copolymers of acrylic acid, the copolymers of methacrylic acid, the homopolymers or copolymers of acrylic acid esters, the homopolymers or copolymers of methacrylic acid esters, the homopolymers or copolymers of acrylic acid amides, homopolymers or copolymers of methacrylic acid amides, copolymers of vinylpyrrolidone, copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymers or copolymers of ethylene, homopolymers or copolymers of propylene, homopolymers or copolymers of styrene, polyurethanes, polyesters and/or polyamides.

The selection of these other substances will be made by the specialist according to the desired properties of the agents. Regarding other optional components and the quantities of these components used, explicit reference is made to the relevant manuals known to the specialist. The additional active ingredients and auxiliary substances are suitably used in the preparations as contemplated herein in quantities of from about 0.0001 to about 25 wt. % each, from about 0.0005 to about 15 wt. %, based on the total weight of the respective agent.

Process for Dyeing Keratin Materials

In the procedure as contemplated herein, agents (a) and (b) are applied to the keratinous materials, to human hair. Thus, agents (a) and (b) are the ready-to-use agents. The agents (a) and (b) are different.

In principle, agents (a) and (b) can be applied simultaneously or successively, whereby successive application is exemplary.

The best results were obtained when agent (a) was applied to the keratin materials as a pretreatment agent and then agent (b) was applied as a colorant.

Therefore, a method for dyeing keratinous material, in particular human hair, including the following steps in the order given is suitable:

-   -   in a first step, applying an agent (a) to the keratinous         material, wherein the agent (a) contains at least one organic         silicon compound selected from silanes having one, two or three         silicon atoms, wherein the organic silicon compound includes one         or more hydroxyl groups and/or hydrolysable groups per molecule,         and wherein the agent (a) further contains at least one         oligoalkylsiloxane, and     -   in a second step, applying an agent (b) to the keratinous         material, the agent (b) including at least one colorant compound         selected from the group including pigments and/or direct dyes.

The agents (a), and (b) are particularly suitably applied within one and the same dyeing process, which means that there is a period of a maximum of several hours between the application of agents (a) and (b).

In a further exemplary embodiment, a method as contemplated herein first the agent (a) is applied, and then the agent (b) is applied, the time between the application of the agents (a) and (b) being at most about 24 hours, suitably at about most 12 hours and particularly suitably at most about 6 hours.

Within the scope of the procedure as contemplated herein, the keratin materials, in particular human hair, are first treated with agent (a). Then the actual colorant (b)—which contains the coloring compounds—is applied to the keratin materials.

Suitably, agent (a) itself does not contain colorants or coloring compounds. A characteristic feature of the pretreatment agent (a) is its content of at least one reactive organic silicon compound and at least one oligoalkylsiloxane. The reactive organic silicon compound(s) (a) functionalize the hair surface as soon as they meet it. In this way a first, still uncolored film is formed. The rate at which this film is formed in the dyeing process can be adjusted to the optimum rate by adding the oligoalkylsiloxane to the agent (a). In the second step of the process, a colorant (b) is now applied to the hair. During application of the colorant (b), the colorant compounds interact with the silane film and are thus bound to the keratin materials. Here, the technical application properties of the resulting dyeing can be further improved by selecting the optimum process conditions.

In the context of a further form of execution, a procedure including the following steps in the order indicated is suitable.

(1) Application of agent (a) on the keratinous material, (2) Allow the agent (a) to act for a period of from about 10 seconds to about 10 minutes, suitably from about 10 seconds to about 5 minutes, (3) if necessary, rinse the keratinous material with water, (4) Application of agent (b) on the keratinous material, (5) Allow the agent (b) to act for a period of from about 30 seconds to about 30 minutes, suitably from about 30 seconds to about 10 minutes, and (6) Rinse the keratinous material with water.

The rinsing of the keratinous material with water in steps (3) and (6) of the process is understood, as contemplated herein, to mean that only water is used for the rinsing process, without any other agents other than agents (a) and (b).

In a first step (1), agent (a) is applied to the keratin materials, especially human hair.

After application, the agent (a) can act on the keratin materials. In this context, application times from about 10 seconds to about 10 minutes, suitably from about 20 seconds to about 5 minutes and especially suitably from about 30 seconds to about 2 minutes on the hair have proven to be particularly beneficial.

In a exemplary embodiment of the method as contemplated herein, the agent (a) can now be rinsed from the keratin materials before the agent (b) is applied to the hair in the subsequent step.

Dyeing's with also good wash fastness were obtained when agent (b) was applied to the keratin materials which were still exposed to agent (a).

In step (4), agent (b) is now applied to the keratin materials. After application, let the agent (b) act on the hair.

The process as contemplated herein allows the production of dyeing's with particularly good intensity and wash fastness even with a short exposure time of agent (b). Application times from about 10 seconds to about 10 minutes, suitably from about 20 seconds to about 5 minutes and most suitably from about 30 seconds to about 3 minutes on the hair have proven to be particularly beneficial.

In step (6), agent (b) (and any remaining agent (a)) is rinsed out of the keratin material with water.

In the context of a further form of execution, a procedure including the following steps in the order indicated is suitable.

(1) Application of agent (a) on the keratinous material, (2) Allow the agent (a) to act for a period of from about 10 seconds to about 10 minutes, suitably from about 10 seconds to about 5 minutes, (3) if necessary, rinse the keratinous material with water, (4) Application of agent (b) on the keratinous material, (5) Allow the agent (b) to act for a period of from about 30 seconds to about 30 minutes, suitably from about 30 seconds to about 10 minutes, and (6) Rinse the keratinous material with water.

In this embodiment, the sequence of steps (1) to (6) suitably takes place within about 24 hours.

Multi-Component Packaging Unit (Kit-of-Parts)

Within the scope of the procedure as contemplated herein, agents (a) and (b) are applied to the keratin materials, i.e., both agents (a) and (b) are ready-to-use agents.

To increase user comfort, the user is suitably provided with all required resources in the form of a multi-component packaging unit (kit-of-parts).

A second subject matter of the present disclosure is therefore a multi-component packaging unit (kit-of-parts) for coloring keratinic material, comprehensively packaged separately from one another.

-   -   a first container including an agent (a), wherein the agent (a)         includes at least one organic silicon compound selected from         silanes having one, two or three silicon atoms, wherein the         organic silicon compound includes one or more hydroxyl groups         and/or hydrolysable groups per molecule, and wherein the         agent (a) further includes at least one oligoalkylsiloxane, and     -   a second container including an agent (b), the agent (b)         including at least one colorant compound selected from the group         including pigments and/or direct dyes.

The organic silicon compounds contained in agent (a) of the kit correspond to the organic silicon compounds that were also used in agent (a) of the method described above.

The oligoalkylsiloxanes contained in agent (a) of the kit correspond to the oligoalkylsiloxanes that were also used in agent (a) of the previously described process.

The colorant compounds from the group of pigments and/or direct dyes contained in agent (b) of the kit correspond to the colorant compounds from the group of pigments and/or direct dyes that were also used in agent (b) of the previously described process.

A second subject of the present disclosure is therefore a multi-component packaging unit (kit-of-parts) for coloring keratinous material, comprehensively packaged separately from one another.

-   -   a first container including an agent (a), wherein the agent (a)         includes at least one organic silicon compound selected from         silanes having one, two or three silicon atoms, wherein the         organic silicon compound includes one or more hydroxyl groups         and/or hydrolysable groups per molecule, and wherein the         agent (a) further includes at least one oligoalkylsiloxane,         wherein organic silicon compound and oligoalkylsiloxane were         disclosed in detail in the description of the first subject         matter of the present disclosure     -   a second container including an agent (b), the agent (b)         including at least one colorant compound selected from the group         including pigments and/or direct dyes, as disclosed in detail in         the description of the first subject matter of the present         disclosure.

The agent (a) contains with the organic silicon compound(s) a class of highly reactive compounds which can undergo hydrolysis or oligomerization and/or polymerization in the presence of water as described above. Due to their high reactivity, these organic silicon compounds form a film on the keratin material.

To prevent premature oligomerization or polymerization and to control the polymerization rate, the agent (a) additionally contains at least one oligoalkylsiloxane.

To avoid premature oligomerization or polymerization, it is of considerable advantage to the user to prepare the ready-to-use agent (a) only shortly before application.

In the context of a further embodiment, a multi-component packaging unit (kit-of-parts) for coloring keratinic material is suitably packaged separately from one another.

-   -   a first container including an agent (a1), wherein the agent         (a1) includes at least one organic silicon compound selected         from silanes having one, two or three silicon atoms, wherein the         organic silicon compound includes one or more hydroxyl groups         and/or hydrolysable groups per molecule, and wherein the agent         (a1) further includes at least one oligoalkylsiloxane, and     -   a second container including an agent (a2), the agent (2)         including water, and     -   a third container including an agent (b), the agent (b)         including at least one colorant compound selected from the group         including pigments and/or direct dyes.

To provide a formulation that is as stable as possible during storage, the agent (a1) itself is suitably packaged with low or no water.

A kit-of-parts packaging unit as contemplated herein the agent (a1)—based on the total weight of the agent (a1)—contains a water content of from about 0.001 to about 10.0% by weight, suitably from about 0.5 to about 9.0% by weight, more suitably from about 1.0 to about 8.0% by weight and very particularly suitably from about 1.5 to about 7.0% by weight.

The agent (a2) contains water. In a exemplary embodiment, a multi-component packaging unit (kit-of-parts) as contemplated herein the agent (a2)—based on the total weight of the agent (a2)—has a water content of from about 15 to about 100% by weight, suitably from about 35 to about 100% by weight, more suitably from about 55 to about 100% by weight, still more suitably from about 65 to about 100% by weight and very particularly suitably from about 75 to about 100% by weight.

Within this version, the ready-to-use agent (a) is now produced by mixing agents (a1) and (a2).

For example, the user can first mix or shake the agent (a1) containing the organic silicon compound(s) with the water-containing agent (a2). The user can now apply this mixture of (a1) and (a2) to the keratin materials—either directly after their production or after a short reaction time of from about 10 seconds to about 20 minutes. Afterwards, the user can apply agent (b) as described above.

In a exemplary embodiment, a multicomponent packaging unit (kit-of-parts) as contemplated herein the agent (a1) contains—based on the total weight of the agent (a1)—one or more organic silicon compounds of the formula (I) and/or (II) in a total amount of from about 1.0 to about 35.0% by weight, suitably from about 3.0 to about 25.0% by weight, more suitably from about 6.0 to about 20.0% by weight and very particularly suitably from about 9.0 to about 15.0% by weight.

In a exemplary embodiment, a multicomponent packaging unit (kit-of-parts) as contemplated herein the agent (a1) contains—based on the total weight of the agent (a1)—one or more organic silicon compounds of the formula (IV) in a total amount of from about 1.0 to about 80.0% by weight, suitably from about 10.0 to about 70.0% by weight, more suitably from about 20.0 to about 60.0% by weight and very particularly suitably from about 30.0 to about 60.0% by weight.

In a exemplary embodiment, a multicomponent packaging unit (kit-of-parts) as contemplated herein the agent (a1) contains—based on the total weight of the agent (a1)—one or more oligoalkylsiloxanes in a total amount of from about 5.0 to about 50.0% by weight, suitably from about 10.0 to about 45.0% by weight, more suitably from about 15.0 to about 40.0% by weight and very particularly suitably from about 20.0 to about 35.0% by weight.

With respect to the other exemplary embodiments of the multi-component packaging unit as contemplated herein, the same applies mutatis mutandis to the procedure as contemplated herein.

EXAMPLES 1. Formulations

The following formulations were produced:

Pretreatment Agent (a)

(a1E) (a1V1) (a1V2) Present Agent (a1) Comparison Comparison disclosure (3-Aminopropyl)triethoxysilan 13.3 g 13.3 g 13.3 g Methyltrimethoxysilane 46.7 g 46.7 g 46.7 g Hexamethyldisiloxane — — 33.3 g Water 40.0 g —  6.7 g Agent (a2) (a2) Ammonia/citric acid ad pH 9.5 Water  100 g

Colorant (b)

(b) Acid Violet 43 2.0 g PVP K 30 (Ashland, ISP, 4.5 g Polyvinylpyrrolidone) Dermacryl 79 (Akzo Nobel, 4.5 g Acrylates/Octylacrylamide Copolymer, CAS-Nr. 129702-02-9) Ammonia (25% aqueous solution) ad pH 10 Water ad 100 g

2. Storage Test

5 g each of the agent (a1V1), (a1V2) and (a1E) were filled into a glass bottle directly after preparation. Each glass bottle was left open for 1 hour. Then, each glass bottle was sealed and stored at 25° C. for 10 weeks.

(a1V1) (a1V2) (a1E) Present Comparison Comparison disclosure 10 Weeks, streaky, jelly streaky, slightly clear solution 25° C. gel-like

3. Application

To prepare the ready-to-use pretreatment agent (a), the indicated amount of stored agent (a1V1), (a1V2) and (a1E), respectively, were mixed with the indicated amount of agent (a2) with shaking. Afterwards the agent (a) was left to stand for 15 minutes. The agent (a) is the ready-to-use agent.

One strand of hair (Kerling, Euronatural hair white) was dipped into the medium (a) and left in it for 1 minute. Afterwards, excess product (a) was stripped from each strand of hair. Each strand of hair was washed out with water. Excess water was scraped off each strand of hair.

Subsequently, the hair strands were each dipped in the agent (b) and left in it for 1 minute. Afterwards, excess agent (b) was stripped from each strand of hair. Each strand of hair was dried and visually evaluated. Then, each hair strand was thoroughly washed (1 min) with water, dried, and visually assessed again.

Specimen 1 2 3 Agent (a1), (a1V1) (a1V2) (a1E) stored 10 weeks,  8.4 g  5 g  8.4 g 25° C.  Agent (a2) 91.6 g 95 g 91.6 g Agent (b) (b) (b) (b) Staining before faint violet + violet ++ violet +++ washing out Staining after almost faint violet +++ washing out uncolored − violet + Color intensity: − = uncolored + = low ++ = average +++ = very good

While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the various embodiments in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment as contemplated herein. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the various embodiments as set forth in the appended claims. 

1. A process for dyeing keratinous material comprising the following steps: applying an agent (a) to the keratinous material, wherein the agent (a) comprises at least one organic silicon compound selected from silanes having one, two or three silicon atoms, said at least one organic silicon compound comprising one or more hydroxyl groups and/or hydrolysable groups per molecule, and said agent (a) further comprising at least one oligoalkylsiloxane, and applying an agent (b) to the keratinous material, the agent (b) comprising at least one coloring compound selected from the group of pigments and direct dyes.
 2. The process according to claim 1, wherein the agent (a) comprises as the at least one organic silicon compound, at least one organic silicon compound of formula (I) and/or (II) R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I), where R₁, R₂ independently represent a hydrogen atom or a C₁-C₆ alkyl group, L is a linear or branched divalent C₁-C₂₀ alkylene group, R₃, R₄ independently of one another represent a C₁-C₆ alkyl group, a, stands for an integer from 1 to 3, and b is the integer 3-a, and wherein in the organic silicon compound of formula (II) (R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II), R5, R5′, R5″, R6, R6′ and R6″ independently represent a C₁-C₆ alkyl group, A, A′, A″, A′″ and A″″ independently of one another represent a linear or branched divalent C₁-C₂₀ alkylene group R₇ and R₈ independently represent a hydrogen atom, a C₁-C₆ alkyl group, a hydroxy C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, an amino C₁-C₆ alkyl group or a group of formula (III) -(A″″)-Si(R₆″)_(d)″(OR₅″)_(c)″  (III), c, stands for an integer from 1 to 3, d stands for the integer 3-c, c′ stands for an integer from 1 to 3, d′ stands for the integer 3-c′, c″ stands for an integer from 1 to 3, d″ stands for the integer 3-c″, e stands for 0 or 1, f stands for 0 or 1, g stands for 0 or 1, h stands for 0 or 1, provided that at least one of e, f, g, and h is different from
 0. 3. The process according to claim 1, wherein the agent (a) comprises as the at least one organic silicon compound, at least one organic silicon compound of formula (I), R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I), where R₁, R₂ both represent a hydrogen atom, and L represents a linear, divalent C₁-C₆-alkylene group, R₃, R₄ independently of one another represent a methyl group or an ethyl group and a stands for the number 3 and b stands for the number
 0. 4. The process according to claim 1, wherein the agent (a) comprises as the at least one organic silicon compound, at least one organic silicon compound of formula (I) selected from the group of (3-Aminopropyl)trimethoxysilane (3-Aminopropyl)triethoxysilan (2-Aminoethyl)trimethoxysilane (2-Aminoethyl)triethoxysilan (3-Dimethylaminopropyl)trimethoxysilane (3-Dimethylaminopropyl)triethoxysilan (2-Dimethylaminoethyl)trimethoxysilane and (2-Dimethylaminoethyl)triethoxysilan.
 5. The process according to claim 1, wherein the agent (a) comprises as the at least one organic silicon compound, at least one organic silicon compound of the formula (II), (R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II), where e and f both stand for the number 1, g and h both stand for the number 0, A and A′ independently represent a linear, divalent C₁-C₆ alkylene group and R7 represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a group of formula (III).
 6. The process according to claim 1, wherein the agent (a) comprises as the at least one organic compound, at least one organic silicon compound of the formula (II) which is selected from the group of 3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine 3-(Triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine 2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol 2-[bis[3-(triethoxysilyl)propyl]amino]ethanol 3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine 3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine, N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine, N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine and/or N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine.
 7. The process according to claim 1, wherein the agent (a) comprises as the at least one organic compound, at least one organic silicon compound of formula (IV). R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV), where R₉ represents a C₁-C₁₂ alkyl group, R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group, R₁₁ represents a C₁-C₆ alkyl group k is an integer from 1 to 3, and m stands for the integer 3-k.
 8. The process according to claim 1, wherein the agent (a) comprises as the at least one organic compound, at least one organic silicon compound of formula (IV) selected from the group of Methyltrimethoxysilane Methyltriethoxysilane Ethyltrimethoxysilane Ethyltriethoxysilane Octyltrimethoxysilane Octyltriethoxysilane Dodecyltrimethoxysilane and/or Dodecyltriethoxysilane.
 9. The process according to claim 1, wherein the agent (a) comprises—based on the total weight of the agent (a)—the at least one organic silicon compounds in a total amount of 0.1 to 20.0% by weight.
 10. The process according to claim 1, wherein the agent (a) comprises—based on the total weight of the agent (a)—the at least one organic silicon compounds of the formula (I) and/or (II) in a total amount of from about 0.1 to about 10.0% by weight.
 11. The process according to claim 1, wherein the agent (a) comprises—based on the total weight of the agent (a)—the at least one organic silicon compounds of the formula (IV) in a total amount of from about 0.1 to about 20.0% by weight.
 12. The process according to claim 1, wherein the agent (a) comprises as the at least one organic silicon compound, at least one linear and/or cyclic oligoalkylsiloxane.
 13. The process according to claim 1, wherein the agent (a) comprises as the at least one organic silicon compound, at least one oligoalkylsiloxane of the formula (V) and/or (VI),

where z is an integer from 0 to 10,

where y is an integer from 1 to
 5. 14. The process according to claim 1, wherein the agent (a) comprises as the at least one organic silicon compound, at least one oligoalkylsiloxane selected from the group of hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.
 15. The process according to claim 1, wherein the agent (a) comprises—based on the total weight of the agent (a)—as the one or more organic silicon compound, one or more oligoalkylsiloxanes in a total amount of from about 0.1 to about 25.0% by weight.
 16. The process according to claim 1, wherein the weight ratio of all organic silicon compounds of the formulae (I), (II) and (IV) contained in the agent (a) to all oligoalkylsiloxanes of the formulae (V) and (VI) contained in the agent (a) is from about 5:1 to about 1:1.
 17. The process according to claim 1, wherein the agent (b) comprises as the at least one coloring compound, at least one coloring compound from the group of pigments selected from the group of colored metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulphides, complex metal cyanides, metal sulphates, bronze pigments and/or from colored pigments based on mica or mica which are coated with at least one metal oxide and/or one metal oxychloride.
 18. The process according to claim 1, wherein the agent (b) comprises as the at least one coloring compound, at least one coloring compound from the group of organic pigments which is selected from the group of carmine, quinacridone, phthalocyanine, sorghum, blue pigments having the color index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigments having the color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with Color Index numbers CI 61565, CI 61570, CI 74260, orange pigments with Color Index numbers CI 11725, CI 15510, CI 45370, CI 71105, red pigments with Color Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and CI
 75470. 19. The process according to claim 1, wherein the agent (b) comprises as the at least one coloring compound, at least one direct dye which is selected from the group of anionic, cationic, and nonionic direct dyes.
 20. The process according to claim 1, wherein the agent (b) comprises as the at least one coloring compound, at least one anionic direct dye selected from the group of Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid Orange 24, Acid Red 14, Acid Red, Acid Red 27, Acid Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and D&C Brown
 1. 21.-26. (canceled) 